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AS & A-Level Chemistry 17 — Synthesis, chromatography and NMR

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Independent Deckloop A Level Chemistry study material aligned with Cambridge International 9701 (2025–2027). Deck 17 of 18: Synthesis, chromatography and NMR. Original explanations, worked applications and practice. Not affiliated with or endorsed by Cambridge International Education.

Chemistry EN A-Level
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Thin-Layer Chromatography (TLC)

Thin-layer chromatography (TLC) is a sensitive analytical technique used to separate non-volatile mixtures. The system consists of a stationary phase, typically a solid support coated with a polar adsorbent like aluminium oxide or silica gel (SiO2\text{SiO}_2), and a liquid mobile phase that flows up the plate via capillary action. Separation relies on the differing relative affinities of the mixture's components for the two phases. Polar molecules tend to interact strongly with a polar stationary phase through hydrogen bonding or dipole-dipole interactions, causing them to adsorb firmly and travel slowly. Conversely, non-polar molecules interact weakly with the stationary phase and are usually more soluble in a non-polar mobile phase, allowing them to travel faster and further up the plate. The distance travelled by a component relative to the solvent front is defined as the RfR_{\text{f}} value. Since the baseline is drawn in pencil to prevent contamination from ink dyes, and the solvent front is marked immediately upon removing the plate, the RfR_{\text{f}} value provides a characteristic metric for identifying substances under specific conditions. Differences in RfR_{\text{f}} values are best explained by evaluating the balance between a component's solubility in the mobile phase and its adsorption to the stationary phase. Equal Rf values under one set of conditions support a possible match but do not prove identity: different substances can co-migrate. Measure the spot centre and solvent front from the same baseline.

Key points

  • The stationary phase in TLC is a solid adsorbent, commonly polar aluminium oxide or silica, coated on a rigid support.
  • The mobile phase is a liquid solvent, which can be chosen to be polar or non-polar depending on the mixture.
  • The retardation factor is calculated as: Rf=distance travelled by spotdistance travelled by solvent frontR_{\text{f}} = \frac{\text{distance travelled by spot}}{\text{distance travelled by solvent front}}.
  • A substance with stronger interactions (e.g., hydrogen bonding) with the stationary phase will have a lower RfR_{\text{f}} value.
  • A substance with higher solubility in the mobile phase will travel further, resulting in a higher RfR_{\text{f}} value.

Worked example

Question

A TLC plate using a silica stationary phase and a non-polar mobile phase separates a mixture of hexan-1-ol and hexane. The solvent front moves 9.5cm9.5 \mathrm{cm}. Predict which compound has the higher RfR_{\text{f}} value, and calculate the distance moved by a spot if its RfR_{\text{f}} is 0.42.

Solution

1. Silica is a polar stationary phase. Hexan-1-ol has a polar hydroxyl group that forms hydrogen bonds with the silica, retarding its movement.

2. Hexane is non-polar, interacts weakly with silica, and is highly soluble in the non-polar mobile phase, so it travels further.

3. Thus, hexane has the higher RfR_{\text{f}} value.

4. For the distance calculation: Distance=Rf×solvent front distance=0.42×9.5 cm\text{Distance} = R_{\text{f}} \times \text{solvent front distance} = 0.42 \times 9.5 \text{ cm}.

5. 0.42×9.5=3.99 cm0.42 \times 9.5 = 3.99 \text{ cm}.

Hexane has the higher RfR_{\text{f}} value. The spot with an RfR_{\text{f}} of 0.42 moved 4.0cm4.0 \mathrm{cm} from the baseline.

Common pitfalls

  • Confusing the effects of solvent polarity. Increasing the polarity of the mobile phase generally increases the RfR_{\text{f}} values of polar components by competing with the stationary phase, rather than making them stick more.
  • Measuring from the bottom edge of the plate instead of the baseline. All distances must strictly be measured from the pencilled baseline where the sample was originally spotted.

Prerequisites

  • Study AS synthesis, polymers and spectroscopy first.
  • Study Aromatic chemistry and advanced mechanisms first.
  • Study Acyl compounds, nitrogen chemistry and polymers first.